CN112823176B - resin composition - Google Patents

resin composition Download PDF

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Publication number
CN112823176B
CN112823176B CN201980066517.1A CN201980066517A CN112823176B CN 112823176 B CN112823176 B CN 112823176B CN 201980066517 A CN201980066517 A CN 201980066517A CN 112823176 B CN112823176 B CN 112823176B
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resin composition
component
group
general formula
thiol compound
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CN112823176A (en
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岩谷一希
新井史纪
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Namics Corp
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Namics Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Abstract

A resin composition, the resin composition comprising: (a) an epoxy resin free of aromatic rings; (B) At least one difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain optionally containing a heteroatom and not containing an ester bond and having a thiol group at the end; and (C) an amine compound.

Description

Resin composition
Technical Field
The present invention relates to a resin composition useful for applications requiring heat curing at a relatively low temperature, specifically, heat curing at about 80 ℃.
Background
In manufacturing an image sensor module used as a camera module for a mobile phone or a smart phone, an adhesive thermally cured at a relatively low temperature, specifically, at a temperature of about 80 ℃ is used. In the case of manufacturing electronic parts such as semiconductor devices, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors, it is preferable to use an adhesive containing a resin composition thermally cured at a temperature of about 80 ℃.
In addition, when two members having different coefficients of thermal expansion are bonded by an adhesive, thermal stress may act on the bonded portion due to a change in ambient temperature, and cracks may occur. An adhesive for joining these members is required to have flexibility of such a degree that it can follow thermal deformation of the members, and the adhesive is a cured product having excellent stress relaxation even after curing.
For example, patent document 1 discloses a resin composition containing a thiol compound having 2 or more thiol groups in the molecule as a resin composition which can be thermally cured at a low temperature to obtain a cured product having a small elastic modulus.
Prior art literature
Patent literature
Patent document 1: international publication No. 2012/093510
Disclosure of Invention
Technical problem to be solved by the invention
However, adhesives mainly composed of polythiol compounds having 3 or more thiol groups in the molecule have many crosslinking points, and may not follow thermal deformation of an adherend due to residual stress in the resulting cured product. In addition, when the polythiol compound having 2 thiol groups in the molecule is a difunctional thiol compound having thiol groups at both ends of an alkyl group such as 1, 4-butanedithiol and 1, 10-decanedithiol disclosed in patent document 1, the volatility is high because of the small molecular weight, and there is a possibility that voids are present in the obtained cured product even when cured at a low temperature of about 80 ℃, and the physical properties of the obtained cured product are lowered.
Accordingly, an object of the present invention is to provide a resin composition capable of curing at a low temperature, capable of obtaining a cured product having excellent stress relaxation without impairing physical properties.
Technical means for solving the technical problems
Means for solving the above technical problems the present invention includes the following aspects.
[1] A resin composition, the resin composition comprising:
(A) An epoxy resin containing no aromatic ring;
(B) At least one difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain optionally containing a heteroatom and not containing an ester bond and having a thiol group at the end; and
(C) An amine compound.
[2] The resin composition according to the above [1], wherein the component (B) is a difunctional thiol compound having an alicyclic structure and a molecular chain containing no ester bond and having a thiol group at the end thereof in the molecule.
[3] The resin composition according to the above [1], wherein the component (B) is a difunctional thiol compound having an aromatic ring structure in the molecule and a molecular chain having an ether bond and no ester bond and having a thiol group at the end.
[4] The resin composition according to the above [1], wherein the component (B) is a difunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3):
[ chemical 1]
In the general formula (B-1), n and m are each independently integers of 1 to 3;
[ chemical 2]
In the general formula (B-2), R 1 、R 2 、R 3 And R is 4 Each independently is a hydrogen atom or a group represented by the following formula (b-1), however, R 1 And R is 2 One of them is a group represented by the following general formula (b-1), R 3 And R is 4 One of them is a group represented by the following general formula (b-1),
[ chemical 3]
In the general formula (b-1), r is an integer of 1 to 3;
[ chemical 4]
In the general formula (B-3), G 1 、G 2 Each independently is through-O-or-CH 2 -a bonded 2-valent group, p, q each independently being an integer from 2 to 5.
[5] The resin composition according to the above [1], wherein the component (B) is a difunctional thiol compound represented by the following general formula (B-4) or (B-5):
[ chemical 5]
In the general formula (B-4), s and t are each independently integers of 3 or 4;
[ chemical 6]
In the general formula (B-5), u and v are each independently an integer of 3 or 4.
[6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of the component (A) is 240 to 1,000.
[7] The resin composition according to any one of the above [1] to [6], wherein the component (A) is an epoxy resin represented by the following formula (A-1) or (A-2):
[ chemical 7]
In the formula (A-1), R 5 Is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer of 1 to 20;
[ chemical 8]
In the formula (A-2), R 6 ～R 9 Each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms.
[8] The resin composition according to any one of the above [1] to [7], wherein the amine compound of the component (C) is at least one amine compound selected from the group consisting of imidazole compounds, tertiary amine compounds and amine adducts.
[9] The resin composition according to any one of [1] to [8], wherein the total number of thiol groups of the difunctional thiol compound of the component (B) is 20 to 100, when the number of all thiol groups in the resin composition is 100.
[10] The resin composition according to any one of [1] to [9], wherein the resin composition further comprises (D) a stabilizer.
[11] The resin composition according to the above [10], wherein the stabilizer of the component (D) is at least one selected from the group consisting of a liquid boric acid ester compound, an aluminum chelate compound and barbituric acid.
[12] An adhesive comprising the resin composition according to any one of [1] to [11 ].
[13] A sealing material comprising the resin composition according to any one of [1] to [11 ].
[14] An image sensor module manufactured using the adhesive as described in the above [12] or the sealing material as described in the above [13 ].
[15] A semiconductor device manufactured by using the adhesive according to the above [12] or the sealing material according to the above [13 ].
Advantageous effects
According to the present invention, a resin composition which can be thermally cured at a low temperature of about 80 ℃ and can give a cured product having excellent stress relaxation without impairing physical properties can be provided.
Detailed Description
Hereinafter, embodiments of the resin composition, the adhesive, the sealing material, the image sensor module, and the semiconductor device according to the present disclosure will be described. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following resin composition, adhesive, sealing material, image sensor module, and semiconductor device.
The resin composition according to the first embodiment of the present invention includes:
(A) An epoxy resin containing no aromatic ring;
(B) At least one difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain optionally containing a heteroatom and not containing an ester bond and having a thiol group at the end; and
(C) An amine compound.
(A) The components are as follows: epoxy resin without aromatic ring
The resin composition contains an epoxy resin containing no aromatic ring as the component (A). Since the epoxy resin does not contain an aromatic ring, the glass transition temperature (Tg) of the resin composition after curing is low and the elastic modulus is low. Therefore, in the case where two members having different thermal expansion coefficients are bonded by an adhesive containing the resin composition according to the embodiment of the present invention, even when the two members bonded to each other expand and contract due to the respective different thermal expansion coefficients due to a change in ambient temperature, the resin composition has flexibility capable of following a change in the members and is excellent in stress relaxation.
In addition, the aromatic ring is a structure satisfying the Siberian style, for example, a benzene ring.
The weight average molecular weight of the epoxy resin of the component (A) is preferably 240 to 1,000. The weight average molecular weight of the epoxy resin of the component (a) is preferably 250 to 1,000, more preferably 260 to 1,000, and still more preferably 270 to 1,000. In the present specification, the weight average molecular weight refers to a value of a calibration curve using standard polystyrene according to Gel Permeation Chromatography (GPC).
The epoxy resin of the component (a) is preferably an epoxy resin containing no ester bond to improve moisture resistance of a cured product formed from the resin composition.
For example, the component (A) is preferably an epoxy resin represented by the following formula (A-1).
[ chemical 9]
In the formula (A-1), R 5 Is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer of 1 to 20.
The epoxy resin represented by the above formula (A-1) is preferably an epoxy resin represented by the following formula (A-1-1) and/or (A-1-2).
[ chemical 10]
In the formula (A-1-1), x is an integer of 1 to 15.
[ chemical 11]
In the formula (A-1-2), y is an integer of 1 to 20.
For example, the component (A) is preferably an epoxy resin represented by the following formula (A-2).
[ chemical 12]
In the formula (A-2), R 6 ～R 9 Each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms.
In addition to the epoxy resin represented by the general formula (A-1) or (A-2), the component (A) may be a hydrogenated bisphenol epoxy resin, an alicyclic epoxy resin, an alcohol ether type epoxy resin, an aliphatic epoxy resin, a cyclic aliphatic epoxy resin, a siloxane type epoxy resin, or the like. Examples of such epoxy resins include hydrogenated bisphenol a epoxy resins, hydrogenated bisphenol F epoxy resins, epoxy-modified polybutadiene, 1, 4-cyclohexanedimethanol diglycidyl ether, and the like.
The resin composition of the present invention may further contain an epoxy resin (aromatic ring-containing epoxy resin) other than the component (a). When the number of the total epoxy groups in the resin composition is 100, the total number of epoxy groups contained in the aromatic ring-free epoxy resin of the component (a) is preferably 20 to 100, more preferably 40 to 100, and still more preferably 50 to 100. (A) The amount of epoxy groups contained in the aromatic ring-free epoxy resin of the component (a) can be calculated by dividing the mass of the aromatic ring-free epoxy resin of the component (a) by the epoxy group equivalent of the aromatic ring-free epoxy resin of the component (a). The ratio of the epoxy groups of the epoxy resin other than the component (a) to the component (a) may be calculated by NMR.
When the epoxy resin other than the component (a) is contained, the amount of the epoxy groups of the epoxy resin other than the component (a) can be calculated by dividing the mass of the epoxy resin other than the component (a) by the epoxy equivalent of the epoxy resin other than the component (a), and the sum of the amount of the epoxy groups of the epoxy resin other than the component (a) and the amount of the epoxy groups of the epoxy resin containing no aromatic ring can be used as the amount of the total epoxy groups in the resin composition.
(B) The components are as follows: difunctional thiol compounds
The (B) difunctional thiol compound contained in the resin composition according to one embodiment of the present invention is at least one difunctional thiol compound selected from the group consisting of the following difunctional thiol compounds: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, optionally contains a heteroatom, does not contain an ester bond, and has a thiol group at the end. (B) The difunctional thiol compound of the component (A) is available from Kagaku Kogyo Co., ltd.
(B) The difunctional thiol compound of the component has a molecular weight of 210 or more, and thus has low volatility, and therefore, for example, when the resin composition is thermally cured at a low temperature of 80 ℃, the difunctional thiol compound does not volatilize, the generation of voids is suppressed, and a cured product maintaining physical properties can be obtained. More preferably, the molecular weight is 280 or more. From the viewpoint of curability, the molecular weight of the difunctional thiol compound of the component (B) is preferably 1,000 or less, more preferably 600 or less.
(B) The difunctional thiol compound of the component (a) has a heteroatom, and has excellent miscibility (compatibility) with the aromatic ring-free epoxy resin of the component (a), and a uniform cured product can be obtained by curing at a low temperature of, for example, 80 ℃. (B) The aromatic ring structure of the component (A) includes a monocyclic aromatic ring structure having 5 or more rings, for example, cyclopentadiene, benzene and the like. Examples of the alicyclic structure include monocyclic alicyclic structures having 5 or more rings, such as cyclopentane and cyclohexene. The heterocyclic structure may be a single ring or multiple rings, may be an alicyclic structure or an aromatic ring structure, or may be a condensed polycyclic structure. Examples of the hetero atom contained in the molecular chain include a sulfur (S) atom and an oxygen (O) atom, and a thioether bond or an ether bond in the molecular chain is preferable. From the viewpoints of miscibility with an epoxy resin and low volatility, the hetero atom in the difunctional thiol compound of the component (B) is preferably a sulfur atom, that is, a molecular chain containing an alicyclic structure and a thioether bond in the molecule and having no ester bond and a thiol group at the end is preferable. In addition, from the viewpoints of miscibility with an epoxy resin and low volatility, the hetero atom is preferably an oxygen atom, that is, a molecular chain containing an aromatic ring structure and an ether bond in the molecule, containing no ester bond, and having a thiol group at the terminal is preferable in the difunctional thiol compound of the component (B). From the viewpoint of adhesion strength to metal, the difunctional thiol compound of the component (B) is more preferably a molecular chain containing an alicyclic structure and a thioether bond in the molecule, containing no ester bond, and having a thiol group at the terminal.
Further, since the difunctional thiol compound of the component (B) has 2 thiol groups, a cured product having a small residual stress and excellent stress relaxation capable of following thermal deformation of an adherend can be obtained when curing the resin composition, as compared with a cured product mainly composed of a trifunctional or higher thiol compound.
Further, the difunctional thiol compound of the component (B) does not contain an ester bond in the molecule, and therefore, even under high temperature and high humidity such as a pressure cooker test (hereinafter also referred to as "PCT"), the hydrolysis resistance is high and the adhesive strength of the obtained cured product can be maintained.
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-1). The difunctional thiol compound shown in (B-1) is available from Kagaku Kogyo Co., ltd.
[ chemical 13]
In the general formula (B-1), n and m are each independently an integer of 1 to 3, and preferably n and m are each 2.
The difunctional thiol compound represented by the above general formula (B-1) is preferably a difunctional thiol compound represented by the following general formula (B-1-1).
[ chemical 14]
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-2). The difunctional thiol compound shown in (B-2) is available from Kagaku Kogyo Co., ltd.
[15]
In the general formula (B-2), R 1 、R 2 、R 3 And R is 4 Each independently is a hydrogen atom or a group represented by the following formula (b-1), however, R 1 And R is 2 One of them is a group represented by the following general formula (b-1), R 3 And R is 4 One of them is a group represented by the following general formula (b-1).
[ 16]
In the general formula (b-1), r is an integer of 1 to 3, preferably 2.
The difunctional thiol compound represented by the above general formula (B-2) is preferably a difunctional thiol compound represented by the following general formula (B-2-1).
[ chemical 17]
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-3). The difunctional thiol compound shown in (B-3) is available from Kagaku Kogyo Co., ltd.
[ chemical 18]
In the general formula (B-3), G 1 、G 2 Each independently is through-O-or-CH 2 -a bonded 2-valent group, p, q each independently being an integer from 2 to 5. G 1 、G 2 Preferably a 2-valent group bonded via-O-, p and q are preferably 3 or 4, more preferably 4.
The difunctional thiol compound represented by the above general formula (B-3) is preferably a difunctional thiol compound represented by the following general formula (B-3-1).
[ chemical 19]
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-4). The difunctional thiol compound shown in (B-4) is available from Kagaku Kogyo Co., ltd.
[ chemical 20]
In the general formula (B-4), s and t are each independently an integer of 3 or 4, preferably 4.
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-5). The difunctional thiol compound shown in (B-5) is available from Kagaku Kogyo Co., ltd.
[ chemical 21]
In the general formula (B-5), u and v are each independently an integer of 3 or 4, preferably 4.
The resin composition according to one embodiment of the present invention may further contain a thiol compound (monofunctional thiol compound, difunctional thiol compound, trifunctional or higher thiol compound) other than the component (B). When the number of all thiol groups in the resin composition is 100, the total number of thiol groups contained in the difunctional thiol compound of the component (B) is preferably 20 to 100, more preferably 40 to 100, and even more preferably 50 to 100. (B) The number of thiol groups contained in the difunctional thiol compound of the component (B) can be calculated by dividing the mass of the difunctional thiol compound of the component (B) by the thiol group equivalent of the difunctional thiol compound of the component (B). The ratio of thiol groups of the thiol compound other than the component (B) to the component (B) can also be calculated by NMR.
In the case of a thiol compound other than the difunctional thiol compound of the component (B), the number of thiol groups of the thiol compound other than the component (B) can be calculated by dividing the mass of the thiol compound other than the component (B) by the thiol group equivalent of the thiol compound other than the component (B), and the sum of the number of thiol groups of the thiol compound other than the component (B) and the number of thiol groups of the difunctional thiol compound of the component (B) can be taken as the number of total thiol groups in the resin composition.
The equivalent ratio of thiol groups (epoxy equivalent: thiol equivalent) to all thiol compounds of epoxy groups of the epoxy resin contained in the resin composition is preferably 1:0.5 to 1:1.5. In the resin composition, when the thiol equivalent is less than 0.5 equivalent or more than 1.5 equivalent relative to the epoxy equivalent of the epoxy resin contained in the resin composition, unreacted epoxy resin or thiol compound remains in the cured product, and therefore the adhesive strength of the resin composition is lowered.
(C) The components are as follows: amine compound
In the resin composition according to one embodiment of the present invention, the amine compound of component (C) is preferably at least one amine compound selected from the group consisting of imidazole compounds, tertiary amine compounds and amine adducts. (C) The amine compound of the component (a) is preferably an amine compound having a function as a curing accelerator for an epoxy resin. For example, the amine compound of component (C) is preferably a solid insoluble at room temperature and is soluble by heating to function as a curing accelerator, and examples thereof include imidazole compounds, tertiary amine compounds, solid dispersion type amine adduct type latent curing accelerators which are solid at room temperature, for example, reaction products of amine compounds and epoxy compounds (amine-epoxy adduct type latent curing accelerators), reaction products of amine compounds and isocyanate compounds or urea compounds (urea type adduct type latent curing accelerators), and the like.
Examples of the imidazole compound include 2-heptadecylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2, 4-diamino-6- (2-methylimidazolyl- (1)) -ethyl-S-triazine, 2, 4-diamino-6- (2 '-methylimidazolyl- (1)') -ethyl-S-triazine-isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N '- (2-methylimidazolyl- (1) -ethyl) -adipodiamide (N, N' - (2-methylethyl) -1-clamp), and the like, but are not limited thereto.
Examples of the tertiary amine compound include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-N-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and primary or secondary amines having a tertiary amino group in the molecule such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, N-. Beta. -hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N-dimethylcarbamic acid, N-dimethylglycine, N-nicotinic acid, N-dimethylglycine, N-methylglycine, N-dimethylhydrazine, alcohols having a tertiary amino group in the molecule, such as N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide, phenols, thiols, carboxylic acids and hydrazides. Examples of the commercially available tertiary amine compound include a frame FXR-1020 and a frame FXR-1020 (manufactured by T & K TOKA, inc.).
Examples of commercially available solid dispersion type amine adduct type latent curing accelerators include HXA9322HP (manufactured by Asahi Kabushiki Kaisha), fair FXR-1121 (manufactured by T & K TOKA, co., ltd.), fair, uta PN-23, fair, PN-F (manufactured by Wei Fair, fu, co., ltd.), and the like. More detailed examples of solid dispersion type amine addition type latent curing agents or latent curing accelerators are incorporated in Japanese patent application laid-open No. 2014-77024.
The content of the amine compound of the component (C) contained in the resin composition varies depending on the kind of the amine compound. From the viewpoint of extending the pot life, the (C) amine compound contained in the resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 35 parts by mass, and even more preferably 1.0 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin contained in the resin composition. In addition, the component (C) may be provided in the form of a dispersion dispersed in an epoxy resin. When the component (C) is used in this form, the amount of the epoxy resin in which the component (C) is dispersed is also contained in the amount of the epoxy resin ((A) and epoxy resins other than the component (A)) in the resin composition of the present invention.
(D) The components are as follows: stabilizing agent
The resin composition according to one embodiment of the present invention may contain a stabilizer of component (D). The storage stability of the resin composition at ordinary temperature (25 ℃) can be improved and the shelf life can be prolonged by the stabilizer containing the component (D). The stabilizer of component (D) is preferably at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and barbituric acid, because of its high effect of improving storage stability at normal temperature (25 ℃).
Examples of the liquid borate compound include 2,2' -oxybis (5, 5' -dimethyl-1, 3, 2-oxaborole) (2, 2' -macy-1, 3, 2-macy-1, 3-oxaborole), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, trilauryl borate, tricetyl borate, tristearyl borate, tris (2-ethylhexyl oxy) borane, bis (1, 4,7, 10-tetraoxaundecyl) (1, 4,7,10, 13-pentaoxatetradecyl) (1, 4, 7-trioxaundecyl) borane, triphenyl borate, and trioctyl borate.
In addition, the liquid boric acid ester compound contained as the component (D) is preferably a liquid boric acid ester compound at room temperature (25 ℃) because the viscosity of the resin composition can be suppressed to be low.
When the liquid boric acid ester compound is contained as the component (D) in the resin composition, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the resin composition.
As the aluminum chelate compound, aluminum triacetylacetonate (for example, ALA: aluminum chelate compound a manufactured by chemical company of shimmy) can be used.
When the aluminum chelate compound is contained in the component (D), it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the resin composition.
When barbituric acid is contained in the component (D), it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the resin composition.
The resin composition of the present invention may further contain, as the other component (E), an inorganic filler selected from the group consisting of silica, alumina, titania, magnesia, glass, talc, calcium carbonate and the like; organic fillers such as acrylic resin, silicone resin, polystyrene resin, and polydivinylbenzene; rubber fillers such as acrylonitrile-butadiene rubber (NBR) and styrene-butadiene rubber (SBR); carboxyl-terminated butadiene nitrile rubber (CTBN), a toughening agent ( agent) such as polybutadiene; at least one additive selected from the group consisting of silane coupling agents, ion capturing agents, leveling agents, antioxidants, defoamers and thixotropic agents ( modifiers). In addition, a viscosity modifier, a flame retardant, a solvent, or the like may be contained.
Method for producing resin composition
The resin composition according to one embodiment of the present invention can be produced by adding the above-described components (a) to (C) and, if necessary, (D) and kneading (mixing). The method for producing the resin composition is not particularly limited. For example, the resin composition according to the present embodiment can be produced by mixing raw materials containing the above-described components (a) to (C) and, if necessary, component (D) with a mixer such as a kneader, a pot mill, a three-roll mill, a hybrid mixer, a rotary mixer, or a twin-shaft mixer. These components may be mixed at the same time, or a part may be mixed first and then the remaining part may be mixed. In addition, the above devices may be used in combination as appropriate.
Adhesive agent
The adhesive according to one embodiment of the present invention uses the above-described resin composition. The adhesive according to one embodiment of the present invention can be cured at a low temperature, and a cured product having excellent stress relaxation can be obtained without impairing physical properties. For example, when two members having different thermal expansion coefficients are bonded using an adhesive according to one embodiment of the present invention, the adhesive has flexibility capable of following thermal deformation of the members even when the members are thermally deformed due to a change in ambient temperature. Specific heat curing conditions are, for example, 60℃to 120 ℃.
Sealing material
The sealing material according to one embodiment of the present invention uses the above resin composition. The sealing material according to one embodiment of the present invention can be cured at a low temperature, and a cured product having excellent stress relaxation can be obtained without impairing physical properties. For example, in the case of sealing a gap between two members using the sealing material according to one embodiment of the present invention, even when the members are thermally deformed due to a change in ambient temperature, the sealing material has flexibility capable of following the thermal deformation of the members. Specific heat curing conditions are, for example, 60℃to 120 ℃.
Image sensor module
An image sensor module according to an embodiment of the present invention is formed using an adhesive or a sealing material containing the above resin composition. The image sensor module also includes camera modules for mobile phones and smartphones. Since the resin composition according to one embodiment of the present invention can be cured at a low temperature, and a cured product having excellent stress relaxation can be obtained without impairing physical properties, it can be suitably used as a resin composition contained in an adhesive or a sealing material used in the assembly of an image sensor module requiring curing at a low temperature of about 80 ℃.
Semiconductor device with a semiconductor device having a plurality of semiconductor chips
The semiconductor device according to one embodiment of the present invention is formed using an adhesive or a sealing material containing the above resin composition. The semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules, electronic devices, and the like in which they are assembled. Since the resin composition according to one embodiment of the present invention can be cured at a low temperature of about 80 ℃ and a cured product having excellent stress relaxation can be obtained without impairing physical properties, the resin composition can be suitably used as a resin composition contained in an adhesive or a sealing material used for assembling a semiconductor device requiring curing at a low temperature.
Examples
The present invention will be specifically described below by way of examples. The present invention is not limited to these examples.
Examples and comparative examples
The components were mixed in the proportions shown in tables 1 to 3 below to prepare resin compositions. In the following table, numerals indicating the blending ratio of the components (a) to (E) each represent parts by mass. The components in tables 1 to 3 are as follows.
Epoxy resin
(A) The components are as follows: epoxy resin without aromatic ring
(A1) YX8000: hydrogenated bisphenol A type epoxy resin, mitsubishi chemical corporation, weight average molecular weight 410, epoxy equivalent: 205g/eq.
(A2) YX7400: an epoxy resin represented by the general formula (A-1-1) (wherein x in the general formula (A-1-1) is 10.3), mitsubishi chemical corporation, weight average molecular weight 870, epoxy equivalent: 435g/eq.
(A3) CDMDG:1, 4-cyclohexanedimethanol diglycidyl ether, weight average molecular weight 264, epoxy equivalent: 132g/eq.
(A4) A coupler (registered trademark) BF1000: epoxy-modified polybutadiene (a substance obtained by epoxidizing the side chain of 1, 2-polybutadiene), ADEKA, a weight average molecular weight of 1,500, epoxy equivalent: 178g/eq.
(A5) TSL9906: represented by the general formula (A-2) (R in the general formula (A-2) 6 ～R 9 Is a methyl group) of the epoxy resin, to sense and case sense. The subscriber company, weight average molecular weight 296, epoxy equivalent 181g/eq.
Component (A'): epoxy resin containing aromatic ring
(A' 6) EXA-850CRP (EPICLON): bisphenol a type epoxy resin, DIC corporation, weight average molecular weight: 344, epoxy equivalent: 172g/eq.
Thiol compound
(B) The components are as follows: difunctional thiol compounds
(B1) Thiol compound 1: difunctional thiol compound represented by the general formula (B-1-1), molecular weight 389, thiol equivalent: 211g/eq.
(B2) Thiol compound 2: difunctional thiol compound represented by the general formula (B-2-1), molecular weight 445, thiol equivalent: 243g/eq.
(B3) Thiol compound 3: difunctional thiol compound represented by the general formula (B-3-1), molecular weight 286, thiol equivalent: 159g/eq.
Thiol compounds other than component (B') (B)
(B' 4) 3, 6-dioxa-1, 8-octanedithiol (1, 8-dimercapto-3, 6-dioxaoctane): manufactured by tokyo chemical industry company, molecular weight 182, thiol equivalent weight 91g/eq.
(B' 5) 1, 10-decanedithiol: manufactured by tokyo chemical industry company, molecular weight 206, thiol equivalent weight 103g/eq.
(B' 6) EPMG-4: tetraethyleneglycol bis (3-mercaptopropionate), manufactured by SC organic chemical Co., ltd., molecular weight 372, thiol equivalent 186g/eq.
(B' 7) PEMP: pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), manufactured by SC organic chemical Co., ltd., molecular weight 489, thiol equivalent 122g/eq.
(B' 8) C3 TS-G:1,3,4, 6-tetra (3-mercaptopropyl) glycoluril, manufactured by Kabushiki Kaisha, molecular weight 432, thiol equivalent 114g/eq.
(C) The components are as follows: amine compound
(C1) HXA9322HP: a solid dispersion type amine adduct type latent curing accelerator (microcapsule imidazole adduct) manufactured by Asahi Kabushiki Kaisha, wherein 1/3 of the weight is microcapsule imidazole adduct and 2/3 is a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and the epoxy equivalent is 180g/eq.
(C2) FXR1121 (a frame): solid dispersion type amine adduct, manufactured by T & K TOKA, inc.
(C3) FXR1020 (a large group), tertiary amine compound, manufactured by T & KTOKA, inc.
(D) The components are as follows: stabilizing agent
(D1) TIPB: triisopropyl borate, manufactured by tokyo chemical industry co.
(E) Other ingredients
(E1) SOE5: silica filler, manufactured by k corporation.
(E2) KBM403: 3-glycidoxypropyl trimethoxysilane (silane coupling agent), manufactured by Xinyue chemical Co., ltd.
Evaluation method
Volatility of
The weight of a metal container having a diameter of 5cm and a depth of 0.5cm was measured. To this was added as a target 1.0g of a thiol compound and left in an oven at 80℃for 1 hour without covering the cover. After cooling, the weight of the metal container was measured, and the volatile component derived from the thiol resin was measured. As a result, the volatile content of 1, 10-decanedithiol was 11%, and the volatile content of 3, 6-dioxa-1, 8-octanedithiol was 27%; in contrast, the volatile components of the other thiol resins containing thiol compounds 1,2, and 3 are all 1% or less.
Adhesive strength
The adhesive strength (shear strength) of the prepared resin composition was measured according to the following procedure. The results are shown in the following table.
(1) Samples were subjected to stencil printing on a 3cm by 4cm SUS (special purpose stainless steel, steel Special Use Stainless) 304 plate at a size of 2mm phi.
(2) A 1.5mm x 3mm aluminum oxide sheet was placed on the printed sample. It was thermally cured using a forced air dryer at 80 ℃ for 180 minutes.
(3) Shear strength was measured by a bench universal tester (1605 HTP manufactured by a company, a strain of academy コ). The resin compositions of examples and comparative examples having a bonding strength of 90N to 180N are shown in Table 1. The resin compositions of examples and comparative examples having a bonding strength of less than 90N are shown in table 2. The resin compositions of examples and comparative examples having a bonding strength of more than 180N are shown in Table 3.
Warp (reverse)
To each of the epoxy resins shown in tables 1 to 3, 0.6 part of thixotropic agent R805 manufactured by the company of diethyl ether was added, and the other components were mixed as shown in tables 1 to 3, to prepare resin compositions. In the following table, numerals indicating the blending ratio of the components (a) to (E) each represent parts by mass. The prepared resin composition was subjected to stencil printing with a square 2cm×2cm stencil (made by yu xing corporation) having a thickness of 125 μm on a polyimide film (a film of yu jen corporation) having a thickness of 5 μm. After 180 minutes of thermal curing at 80 ℃, it was left overnight in an environment at 25 ℃. The portion printed with the cured product was cut out to prepare a 2cm×2cm sample. The distance from the horizontal plane to the maximum height was measured as the warpage amount with the convex surface facing upward by a measuring microscope. From the viewpoint of stress relaxation, the warpage amount is preferably 4.0mm or less.
Hydrolysis resistance
When the resin composition contains an ester bond-containing compound, hydrolysis is performed at high temperature and high humidity, and the resin cured products (the samples having measured the warpage amounts) of the compositions of comparative examples 3 and 4 are continuously subjected to PCT conditions (121 ℃ and 2 atmospheres) for 10 hours, the resin cured products liquefy, and the hydrolysis resistance is poor. On the other hand, the compositions of example 16 and example 17 were found to be free from abnormalities in the appearance of the cured resin.
TABLE 1
TABLE 2
TABLE 2
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The cured products obtained from the resin compositions of examples 1 to 20 were excellent in hydrolysis resistance and low volatility, and the cured products after curing had no voids.
As shown in table 1, the cured products obtained from the resin compositions of examples 1 to 11, in which the adhesive strength of the resin compositions was 90N to 180N, were less than 2.1mm in warpage, and the warpage was suppressed as compared with comparative example 1. From this result, it was confirmed that the resin compositions of examples 1 to 11 have small residual stress, and after bonding two members having different thermal expansion coefficients, even when the two members expand and contract due to a change in ambient temperature, they have flexibility capable of following the change in the two members, and are excellent in stress relaxation. On the other hand, the cured product obtained from the resin composition of comparative example 1, which had a bonding strength of 90N to 180N, had a warpage of more than 2.1mm. The thiol compound contained in the resin composition of comparative example 1 has a small molecular weight and volatility, and bubbles are generated in the resin composition during curing, so that voids are present in the obtained cured product. In example 11, an aromatic ring-containing epoxy resin was used in combination, and the adhesive strength and the warpage inhibition were also good.
As shown in table 2, the warpage of the cured products obtained from the resin compositions of examples 12 to 14, in which the adhesive strength of the resin composition was less than 90N, was 1.2mm or less, and the warpage was suppressed as compared with comparative examples 2 and 3. From this result, it was confirmed that the residual stress was small, and after bonding two members having different thermal expansion coefficients, even when the two members were expanded and contracted due to the change in ambient temperature, the flexibility was able to follow the change in the two members, and the stress relaxation was excellent. On the other hand, the cured products obtained from the resin compositions of comparative examples 2 and 3, in which the adhesive strength of the resin composition was less than 90N, had a warpage of more than 1.2mm. The thiol compound contained in the resin composition of comparative example 2 has a small molecular weight and volatility, and bubbles are generated in the resin composition during curing, so that voids are present in the obtained cured product. Since the thiol compound contained in the resin composition of comparative example 3 contains an ester bond, the possibility of hydrolysis is high, and the decrease in adhesive strength at high temperature and high humidity is predicted. In example 14, the combination of 2 components (a) was used, and the adhesive strength and warpage were also well suppressed.
As shown in table 3, the warpage of the cured products obtained from the resin compositions of examples 15 to 20, in which the adhesive strength of the resin composition was greater than 180N, was less than 4.0mm, and the warpage was suppressed as compared with comparative examples 4 and 5. From this result, it was confirmed that the residual stress was small, and after bonding two members having different thermal expansion coefficients, even when the two members were expanded and contracted due to the change in ambient temperature, the flexibility was able to follow the change in the two members, and the stress relaxation was excellent. On the other hand, the cured products obtained from the resin compositions of comparative examples 4 and 5, in which the adhesive strength of the resin composition was greater than 180N, had a large warpage of greater than 4.0mm. From the results, it was predicted that the cured products obtained from the resin compositions of comparative examples 4 and 5 had residual stress, and that when the two members were bonded together, there was no flexibility capable of following the change in the two members due to the influence of temperature. Further, since the thiol compound contained in the resin composition of comparative example 5 contains an ester bond, the possibility of hydrolysis is high, and the decrease in adhesive strength under high temperature and high humidity is predicted. In addition, examples 16 to 19 are examples in which the thiol compound other than the component (B) and the component (B) are used in combination, and the adhesive strength and the warpage are also excellent.

Claims (14)

1. A resin composition, the resin composition comprising:
(A) An epoxy resin containing no aromatic ring;
(B) At least one difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain optionally containing a heteroatom and not containing an ester bond and having a thiol group at the end; and
(C) An amine compound having a structure represented by the formula,
wherein the total number of epoxy groups contained in the aromatic ring-free epoxy resin of the component (A) is 20 to 100 when the number of total epoxy groups in the resin composition is 100,
wherein the total number of thiol groups of the difunctional thiol compound of the component (B) is 20 to 100 when the number of all thiol groups in the resin composition is 100.
2. The resin composition according to claim 1, wherein the component (B) is a difunctional thiol compound having an alicyclic structure and a molecular chain containing no ester bond and having a thiol group at the end thereof in the molecule.
3. The resin composition according to claim 1, wherein the component (B) is a difunctional thiol compound having an aromatic ring structure in the molecule and a molecular chain having an ether bond and no ester bond and having a thiol group at the end.
4. The resin composition according to claim 1, wherein the component (B) is a difunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3):
[ chemical 22]
In the general formula (B-1), n and m are each independently integers of 1 to 3;
[ chemical 23]
In the general formula (B-2), R 1 、R 2 、R 3 And R is 4 Each independently is a hydrogen atom or a group represented by the following general formula (b-1)And R is 1 And R is 2 One of them is a group represented by the following general formula (b-1), R 3 And R is 4 One of them is a group represented by the following general formula (b-1),
[ chemical 24]
In the general formula (b-1), r is an integer of 1 to 3;
[ chemical 25]
In the general formula (B-3), G 1 、G 2 Each independently is through-O-or-CH 2 -a bonded 2-valent group, p, q each independently being an integer from 2 to 5.
5. The resin composition according to claim 1, wherein the component (B) is a difunctional thiol compound represented by the following general formula (B-4) or (B-5):
[ chemical 26]
In the general formula (B-4), s and t are each independently integers of 3 or 4;
[ chemical 27]
In the general formula (B-5), u and v are each independently an integer of 3 or 4.
6. The resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the component (A) is 240 to 1,000.
7. The resin composition according to any one of claims 1 to 5, wherein the component (A) is an epoxy resin represented by the following formula (A-1) or (A-2):
[ chemical 28]
In the formula (A-1), R 5 Is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer of 1 to 20;
[ chemical 29]
In the formula (A-2), R 6 ～R 9 Each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms.
8. The resin composition according to any one of claims 1 to 5, wherein the amine compound of component (C) is at least one amine compound selected from the group consisting of imidazole compounds, tertiary amine compounds and amine adducts.
9. The resin composition according to any one of claims 1 to 5, wherein the resin composition further comprises (D) a stabilizer.
10. The resin composition according to claim 9, wherein the stabilizer of the (D) component is at least one selected from the group consisting of a liquid borate compound, an aluminum chelate compound and barbituric acid.
11. An adhesive comprising the resin composition according to any one of claims 1 to 10.
12. A sealing material comprising the resin composition according to any one of claims 1 to 10.
13. An image sensor module manufactured using the adhesive according to claim 11 or the sealing material according to claim 12.
14. A semiconductor device manufactured using the adhesive according to claim 11 or the sealing material according to claim 12.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1232849A (en) * 1998-04-22 1999-10-27 奥依列斯工业株式会社 Lubricating coating, sliding structure and sliding bearing device using the same structure
CN103282401A (en) * 2011-01-05 2013-09-04 纳美仕有限公司 Resin composition
JP2016079313A (en) * 2014-10-20 2016-05-16 京セラケミカル株式会社 Repairable adhesive composition and electric and electronic component
CN106062030A (en) * 2014-03-17 2016-10-26 纳美仕有限公司 Resin composition
CN108026252A (en) * 2015-09-30 2018-05-11 纳美仕有限公司 Composition epoxy resin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2911157B2 (en) * 1990-01-17 1999-06-23 横浜ゴム株式会社 Epoxy resin composition
JP3953134B2 (en) * 1997-02-21 2007-08-08 三井化学株式会社 New plastic lens containing selenium and method for producing the same
JP4000666B2 (en) * 1998-04-22 2007-10-31 オイレス工業株式会社 Lubricating paint
US11807596B2 (en) * 2017-10-26 2023-11-07 Shikoku Chemicals Corporation Thiol compounds, synthesis method therefor, and utilization of said thiol compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1232849A (en) * 1998-04-22 1999-10-27 奥依列斯工业株式会社 Lubricating coating, sliding structure and sliding bearing device using the same structure
CN103282401A (en) * 2011-01-05 2013-09-04 纳美仕有限公司 Resin composition
CN106062030A (en) * 2014-03-17 2016-10-26 纳美仕有限公司 Resin composition
JP2016079313A (en) * 2014-10-20 2016-05-16 京セラケミカル株式会社 Repairable adhesive composition and electric and electronic component
CN108026252A (en) * 2015-09-30 2018-05-11 纳美仕有限公司 Composition epoxy resin

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